Unexpected Pd-catalyzed hydrogenation of phenol to 2-cyclohexene-1-one: enhanced activity and selectivity assisted by molecular oxygen

Addition of O(2) enables the liquid-phase hydrogenation of phenol using H(2) at low temperatures under atmospheric pressure with an unexpected selectivity towards 2-cyclohexene-1-one rather than cyclohexanone. As a catalyst, as-synthesized Pd/MCM-41 including the residual templates within the mesoporous channels exhibits a prominent positive effect on the catalytic performance.     

Optimization of ionic conductivity in solid electrolytes through dopant-dependent defect cluster analysis

Atomistic simulation based on an energy minimization technique has been carried out to investigate defect clusters of R(2)O(3) (R = La, Pr, Nd, Sm, Gd, Dy, Y, Yb) solid solutions in fluorite CeO(2). Defect clusters composed of up to six oxygen vacancies and twelve accompanied dopant cations have been simulated and compared. The binding energy of defect clusters increases as a function of the cluster size. A highly symmetric dumbbell structure can be formed by six oxygen vacancies, which is considered as a basic building block for larger defect clusters. This is also believed to be a universal vacancy structure in an oxygen-deficient fluorite lattice. Nevertheless, the accurate positions of associated dopants depend on the dopant radius. As a consequence, the correlation between dopant size and oxygen-ion conductivity has been elucidated based on the ordered defect cluster model. This study sheds light on the choice of dopants from a physical perspective, and suggests the possibility of searching for optimal solid electrolyte materials through atomistic simulations.     

Diastereoselective synthesis of 3,3-disubstituted oxindoles from atropisomeric N-aryl oxindole derivatives

Diastereoselective synthesis of 3,3-disubstituted oxindoles has been examined by transformations involving nucleophilic addition, alkylation, and cycloaddition using chiral racemic N-aryl oxindoles bearing C–N axial chirality. The most striking features of this approach are high diastereoselectivities (up to >95:<5) when using ortho-monosubstituted N-aryl oxindoles and easy removal of the p-(benzyloxy)aryl moiety in the axially twisted amides by a mild two-step sequence.     

Stereocontrolled synthesis of substituted chiral piperidines via one-pot asymmetric 6π-azaelectrocyclization: asymmetric syntheses of (-)-dendroprimine, (+)-7-epidendroprimine, (+)-5-epidendroprimine, and (+)-5,7-epidendroprimine

The asymmetric one-pot 6π-azaelectrocyclization of alkenyl vinyl stannane, ethyl (Z)-2-iodo-4-oxobutenoate, and (-)-7-isopropyl-cis-aminoindanol in the presence of a Pd(0) catalyst stereoselectively produced the tetracyclic aminoacetal compounds, resulting from the four-bond formation accompanying by controlling the stereochemistry at the two asymmetric centers. The produced cyclic aminoacetals can be regarded as synthetic precursors of substituted chiral piperidines, and the syntheses of 2,4- and 2,4,6-substituted piperidines were realized from the obtained aminoacetals by the stereoselective hydrogenation of the double bond conjugated with the C-4 ester group and alkylation at the aminoacetal moiety. In addition, the stereoselective synthesis of an indolizidine alkaloid, (-)-dendroprimine, and its three stereoisomers, (+)-7-epidendroprimine, (+)-5-epidendroprimine, and (+)-5,7-epidendroprimine, were achieved.     

Search of Kaonic Nuclear States at the SuperB factory

The search of nuclear bound states of ${\bar{K}}$ in few-body nuclear systems such as K ^? pp, can be extended from the nuclear medium to the vacuum, using the glue-rich ${\Upsilon(1S)}$ decays at B-factories. Here the possibility for such a measurement at the future SuperB factory is discussed.     

Low‐temperature and high-pressure apparatus developed at ISSP,University of Tokyo

A high-pressure apparatus with cubic-anvil device has been successfully working for more than 10 years at low temperatures down to 2?K under quasi-hydrostatic pressure up to 10?GPa in study of solid-state physics. Main parts of it are composed of a set of compact cubic-anvils, a top-loading high-pressure cryostat and a 250?ton press. All the particulars of the cubic-anvil apparatus are given, including pressure calibrations at low temperature.     

Pressure effect on the magnetic phase diagram of Hf1-xTaxFe2 alloys

Abstract

The lattice constants of Hf_1-xTa_xFe₂ with C14 structure were measured at room temperature under pressure up to 5 GPa. The magnetic phase diagram obtained as a function of pressure was compared with that obtained as a function of Ta concentration x. It is shown that changes in lattice constants by applying pressure and /or by substituting Ta for Hf affect remarkably the magnetic phase stability, which is consistent qualitatively with a recent theoretical prediction based on the local spin density approximation.     

X-ray diffraction studies on oxide-superconductors under pressure by a new X-ray detection system

Abstract

A new high pressure x-ray diffraction system has been developed, which consists of a diamond anvil cell, an imaging plate as a detector and an 18 kW rotating anode type generator. By this system we found an anisotropic compression and anomalies in linear compressibility for the Bi-oxide superconductors.